Process for the pyrolysis and gasification of hydrocarbonaceous materials



Apnl 28, 1959 M. P. SWEENEY ,8

PROCESS FOR THE PYROLYSIS AND GASIFICATION OF HYDROCARBONACEOUSMATERIALS Z'Sheets-Sheet 1 Filed Feb. 17, 1956' Elm l EPARAT/ON F/ G' I27 VESSEL v V V 26 v /5 4 Z 7 25 v 9 /0 47 ie BURNER v HEAT 5 EEXCHANGE}? 3 l8 2 aw IIVM/Q 2 V PREHEATER sum 5 I 9 30 34 I, I I V22 v20 1 L \V/ 2/ HYDROGARBON FEED CYCLONE SEPARATOR l4 3 2/8 zzr 220a i 25BURNER 220 FRACUOIVATOR INVENTOR.

Maxwell Pafn'c/r Sweeney BYh/s al/orneys AMMM April 28, 1959 M P.SWEENEY 2,884,368

PROCESS FOR THE PYROLYSIS AND GASIFICATION OF HYDROCARBONACEOUSMATERIALS Filed Feb. 17, 1956 2 Sheets-Sheet 2 QAS/F/ER PRODUCT CO-K GASand GASQQENE /3// 303 3 5 645 0/1. I -334 6A5! F/ER 0 5 5 IN V EN TOR.

Maxwell Parr/"ck Sweeney Y his affarn eys MAM.

RECYCLE Recycle 60 United States Patent PROCESS FOR THE PYRGLYSIS ANDGASIFICA- TION OF HYDROCARBONACEOUS MATERIALS Maxwell Patrick Sweeney,Philadelphia, Pa., assiguor to United Engineers & Constructors Inc.,Philadelphia, Pa., a corporation of Delaware Application February 17,1956, Serial No. 566,205

17 Claims. (Cl. 208-53) This invention pertains to a method for theproduction of valuable gaseous, liquid, and solid products from lowervalue hydrocarbonaceous materials, and particularly to a method for thepyrolysis of hydrocarbonaceous substances, in the presence of finelydivided solid material, without the disadvantages normally associatedwith the use of such material.

The invention is of use in many diflFerent applications; for example inthe production of valuable gaseous and liquid products and coke frompetroleum residues and low value gaseous hydrocarbons, in thegasification and carbonization of coal, lignite and peat and inpetroleum refining.

Prior to the present invention a number of processes have been suggestedfor converting lower value hydrocarbonaceous materials, such as lowerparaffins, residual fuel oils and coal, to more valuable gaseous andliquid products, and coke.

In general, these processes have been run at three different temperatureranges, below about 1100" F., above 1800" F. and in the intermediaterange between about 1100 F. and about 1800 F.

Below about 1100 F., the products are primarily lower molecular weightnormally liquid paraflinic hydrocarbons.

Above about 1800 F. the products are largely carbon and normally gaseousmaterials having a high acetylenic content.

In the range between about 1100 F. and about 1800 F. the proportion ofaromatic substances is large, increasing with increasing temperature,above about 1100" F. and reaching a maximum around 1500 F. Thesearomatic materials have a high sale value and in most cases are the mostdesirable product. However, many of the aromatics so produced tend topolymerize in the presence of other pyrolysis products and at thetemperatures in question, i.e. 1100 F. to 1800 F., to produce highmolecular weight liquid pitch.

The question how best to control the several reactions involved and tocollect the large variety of difierent products formed has given rise toa number of different techniques for conducting pyrolysis processes inthis temperature range and for furnishing the heat necessary for thepyrolysis.

It has been proposed, for example, to charge the low costhydrocarbonaceous feed to a fluidized bed of finely divided solidsmaintained at pyrolysis temperature and to conduct all of the crackingin the bed. The difficulty with this technique is that it is inherentlyinflexible. Reaction time, temperature, and other conditions vary withdiflerent feed materials and products, and it is desirable to have anapparatus capable of handling a variety of different feeds to make avariety of different products. Vessels suitable for holding a fluidizedbed must, however, be designed for a limited range of operatingconditions, and are not easily altered to diflferent conditions.Moreover, in many instances it is desirable to quench the iceintermediate products and prevent the pyrolysis feaction from going tocompletion. This cannot conveniently be done with a single fluidizedbed. I

It has also been proposed to conduct the pyrolysis reaction in a hotmoving streamof gases and entrained solids and then deliver the reactedstream into a suitable separation device, such as a cyclone separator,where the va-porou-s pyrolysis products would be separated from thesolids. Processes of this type have the drawback that they are difficultto control to give products of uniform composition. Moreover, where thepyrolysis products are quenched, as by spraying oil into the sep arationdevice, high molecular Weight pitch molecules deposit on the walls ofthe separator, or pass out of the separator and deposit in downstreamapparatus. In either case, removal of the high molecular material is anexpensive operation.

In a large number of prior techniques the heat necessary for pyrolysishas been furnished by burning the solid coke or char produced. The mostusual technique is to withdraw solid pyrolysis product from the reactionzone where it is formed, and burn part of it in a heater, and often in afluidized bed, to heat the unburned remainder which is then reburned tothe reaction zone.

This technique is open to several objections. The ash produced containsoxides of vanadium, nickel and iron. Since the unburned solids arecontinuously recirculated, this ash and the oxides contained thereinbuild up in the system and cause serious problems of corrosion,particularly at temperatures of say 1400 F. and above.

In addition to problems of corrosion, concentration of metallic oxidesin the fluidized solids causes very serious difficulties of temperaturecontrol. Thus at a reactor temperature of say 1400" F., and under thereducing conditions maintained in the reactor, the metal oxides give upa substantial portion of their oxygen. They are later reoxidized in theheater. The oxidation reaction in the heater is highly exothermic andthe reduction reaction in the reactor is endothermic, causing the heaterto overheat excessively and the reactor to cool off excessively, andmaking it difiicult to maintain a proper temperature in the reactorwithout having the heater operate at an excessively high temperature.

It has also been found that the reduced oxide containing particlesformed in the reactor tend to stick to each other and to the reactorsurfaces, causing difiiculties in fluidization.

It may further be pointed out that while prior pyrolysis systems of thetypes described have been utilized to treat petroleum residues, topresent knowledge no attempt has been made to replace basic refineryequipment, such as atmospheric and vacuum distillation equipment orthermal and catalytic cracking equipment with such systems. This is sodespite the fact that such conventional basic equipment presents a verylarge cost element, particularly in smaller plants of say 5000 to 50,000bbL/day capacity.

It is an object of the present invention to provide a more economicmethod and apparatus for the production of high value solid, liquid, andgaseous products from low value hydrocarbonaceous materials, than hashitherto been available.

It is a further object of the invention to provide a method andapparatus of the class described in which a maximum amount of liquidaromatic products can be obtained.

It is another object of the invention to provide an economic method andapparatus of the class described using a mass of finely divided solidcarbonaceous materials.

It is a further object of the invention to provide a process andapparatus of the class described in which the necessary heat can bedrawn from the combustion oti eqlge f or rr ecl during the process,under conditions which are more easily controlled than has hitherto beenpossible.

Itwis. a furthernobject. of. theinvention to provide a method and.apparatus .of' the class described in which 'It is a furtherrobjectoffthednvention to provide a method and apparatus of the class.described in which either hydrocarbon oil, or coal, or both, can be usedsiehdstwk;

lt is' a further object of the invention to provide a method andapparatus of the class described in which sueeessiv ,eXpOS1 re ofashrcontaining material to oxidizset! educi a o d ti s isrminimized-It'is a further object of the invention to provide a' pgocess and.apparatus of the class described in which corrosive oxides are easilyremoved from the system.

I is. t l n tha bj ct f e nv nt t Provide msthc s nd. pparatus. .-v hfinin ipe simpler-arm s pe i an. hos P ently av lable...

.Aeeor ng to the inyention, theseand other objects trE'IbeEyQeenabouullOQ" F, and about 1800 and, prsi rahly qabetw en bo .0 nd b tstpar ally p rol se a d f e re m, y charge,

"25 anc iienu ained finely divided solids, delivering the combi'ne reamof hot gases, solids andfeed to a fluidized Pals. iv de sqlids removingp u p ymlrsi f omsa d Tl auslacf l fluid zed eds-r t y o s emrsramrecint e manne nd ca e Pr v s a nd of temperature for-a relativelyextendedtime without undue enlargement of'equipment, until theirpyrolysis: is uniormly postula d If on the other ha nd,' the productsare quenched either by n aintaining the bed at a low temperature, or byusing a quenching spray as described more fully below, the fliiidize'dbed'providesa large surface area for incompIeteIY pyrQIysedliquids todeposit upon, I preventing their-depositing on andfouling I downstreamapparatus.

'The solid 'particles in the hot stream and in thefluidized' bed; arepreferably, but not necessarily, the COkQf'OF'ChHl' produced by thepyrolysis. If desired, this; coke may be augmented or replaced by othersolid carbonaceous material such as coal, lignite, oil shale or thelike,-or char or coke from some external source.

It-is also within the scope of the invention to use av more inertmaterial, for example, sand. Entrained in the moving stream, the solidparticles serve to bring the stream gasesto the desired temperature,either by heating or by cooling them. The particles also provide a u fce-upon hichccke me y-pyro y f the flagran -d posit.

'I'he ,hydrocarbonaceous=materials which can be used.

as feed in the novel process include such materials. as,

for example,,- coal, oil,sha,le, lignite, peat, residualfuel oil ;such;as Bunker C fuel oil, coke oven lay-product: Fs-l 934d? e asldltqedncmde ;oil-, virgin distillate z-gass ned by heating ahydrocarbonaceous feed stream i d t sa but. moving s r m fj s p rolysismay be kept at a high easily controlled '45 ofthermalflywheel'whichpermits a.rnore. stable and easily controlledpyrolysis; Thus, heavyliquid; products oils, catalytic recycle gas oils, kerosenes, naphthene,and lower parafiins having two or more carbon atoms in the molecule,such as propane, butanes, and ethane.

The gaseous stream containing entrained solids into which thehydrocarbon feed is introduced, may be derived from several sources.Where the primary purpose is to produce a high heating value utilitygas, the entraining gas.is.preferably one which may easily be separated"from the gaseousproducts of pyrolysis, or else which will not detractfrom the value of the product. Such. gases may for example be steam orrecycled product gas.

Where, on the other hand, a diluted product gas is acceptable, 7 theentraining gases may be products of combustion, e.g. CO and/ ornitrogen.

The temperature-,at'which vthe pyrolysis is conducted will vary to someextent with the materials being reacted and with the products desired.Generally, however, as indicated above, it will. be between about 1100F. and aboutlfiOO" FL, preferablyrbetween about 1100 F. and aboutlYOOfF. Pressure is not considered critical andmaybe atmospheric or as highas, for example, 2050 p.s,i,g. Reaction time mayvary from say about 0.1.to about 5 "seconds.

Preferably, the heat necessary forpyrolysis is furnished" byburningfinely divided coke or char produced in the pyrolysis reaction.In;a preferred form of-the invention, the coke is burned in a slaggingtype combustion; device. By this is meanta combustiondevice so designedthat theash is,converted to a liquid slag which may be drained-away,rather than passing off overhead to gatherin downstream products andapparatus. Such combustion, devices include those having'cycloniccombustion chambers in,,which the finely divided fuel is burned'ina,vortically moving body of hot gases. Furnaces of this i type are wellknown in the artandare-described, for example in Patents Nos. 836,145,836,219; and2,357,30l. Th'ey;-are cornmonly referred toas cyclonefurnaces. Where the solid material entrained-in the gases priortofeedintroductionis not carbonaceous, it will of course not be possibleto use a slagging type burner.

Itiisalso within the, scope of the invention to obtain the heatnecessary for pyrolysis in-whole orin part from sources other than thecoke produced. Thus, where the coke has a-sale value higher thanavailable external fuels, it may be recovered and in its place-the cheapexternal" fueLmay be burned in any type of a conventional burner.Injcertain cases, the value, of the coke may be-higher than the fuel gasproduced -by pyrolysis and there the fuel-gas may beburned in place ofor in partial replace-- ment of the coke. 1

The way in which the heat of pyrolysis is transferred from'its-source tothe ,hydrocarbonaceous feed varies." Preferably, however, where thesolid products of pyrolysis areburned to producethe necessary heat, noportion of *the solids introduced intoa zonewhere substantial oxidationtakes place .is reintroduced into the reaction zone; In thispway,building up of'metal oxidesv in.the. system is; avoidedr In oneembodiment, hot gaseous products of combustion drawn from a burner aremade to entrain finely divided solids having a lower temperature than-the hot gases, and it is to this stream that the hydrocarbonaceous feedis added This embodiment is simple anddirectand requires-a minirnum ofequipment.

In' asecond-embodiment, hot gaseous products of' combustion drawn fromaburner are used to heat up a-:mass-of-finelydivided solids, which isthen separated from the products of combustion and entrained in anotherstream ofgases to which is charged the hydrocar-;

bonaceousnfeed;v This :other gas stream maybe, for ex-' ample-steamerrecycled'productrgas. Thesecond em, bodiinent: has the ,-advantage: of ravoiding contamination;- of-;the gaseousproducts of pyrolysis by-inertcomponents suchrasyCQ Such;co-ntamination ;would, result werev hezhocprnucts iofi-combustionzbroughtdirectly into corn; tact: withathe feeds;

ph nd a final xotherm c p ase. the endothermic p ,the hydrocarhonaceousfeed eenv'ertedintqsub ces -l: '|'e lieyecl to consist of free radicalsand un'sa'tu d gpmpdnnus", which have higher enthalpies than the nailpioduct's'. In "the second stage, these'interrnediate high enthalpy,substances rfeconibinetofoiin the final pion ers" and in" sodoiiig' rease heat. V In the p'resent" r cess, ne i al endothermic phase or the"cracking reaction ma be carried out before the mixture of the gases andsolid particles reaches the fluidized e an the exothe hfi portion maythen be 651; ed out in the iiuidrzed b eidj this arrangement, the heatof reaction aid's in maintaining thefbed, with its relatively largecross-sectional "area and volume, at reabfiofi tem e at e I. j i f i Aer t e y b t por i ns f, e; v ti i.my be carried to completion beforethe reactants reach the fluidized bed and the may be maintained at arela-' tively temperature to quench the reaction products andvpreventthe formation of undesirable materials; By ehqh i i n i man er, 'i el lb iten' s Q high ba l ai r sa ase t 9n the =P t l 9 PQk'e andxarqt nremq di mm th W a team W e e they, w uld tandfiq dsaa i i r fer. l eand. 15 15 usnt .d s ill i men -v, f n w rys h some? ai f he,b d .my1bem in a a s trby w h: drawing solid materialfrom the bed heating orcooling it, as in a heat exchanger, and retu rningit to the bed. It is;f. soi eda so qs n l to ha ei h r, the 951 thermic or the exothermicparts split between the reaction stream and the fluidizedbed, H 1 V I 2In; another aspect of the invention, especially useful where arelatively heavy hydrocarbonacequs feed, such as Bunker C fuel oil orcoke oven tar is charged to a hot moving stream of gases and entrainedsolids, materials having a molarH/ C (hydrogen/carbon) ratio, rela; tiveto the hydrocarbonaceousfeed, rnay "be added to the hot stream beforethe ,feed itself is introduced. Such materials may include, for example,hydrogen, or hydrocarbons such .as methane, ethane, ethylene, propane.propylene, and butane ;By ,using such additions, the proportion of lowerboiling materials in ,the. Pyro lysis pro dnot is increased and, theproportion of pitchis decreased. In particular where butaneis used, theproportionof valuablebutadiene is increased. In addition, sulphur whichwould normally remain ,in the coke or char resi due is'carried overheadas H28, increasing the value of the char or coke.

The materialsadded may be obtained from sources outside the pyrolysissystem. However, the fixed gases produced by pyrolysis contain materialshaving a high H/C ratio and preferably these gases, or a portion ofth'enji, are recycled and added' to the hot stream.,.

' Except in the case wherejthe material added consists principally ofhydrogen, it is generally desirable to inject the added material at apoint on the hot gaseous e11 trained soli'dslstream where thetemperature, of thehot stream is suffi cient to at least" partiallycrack the added substance; for exam le at between about 1500? F. andabout 170051 In this way, additional valuable prodnets are formed and ahigh partial pressure of hydrogen is orea'ted 'in the zone Wherepyrolysis of the main feed material is to' be carried out. A highpartial pressure of hydrogen enhances the efiEects noted above, namely adoc e in the production of pitch, an increase inthe' trjty of lowerboiling materials, and a more valuable res1 It is also within the scopeof the invention, where the sagas b d, h ijs" medium may be" water; asis iffejably'a liquid hydro ar bon, suchfor example ss as" The amount ofoil is preferably re ulated" so' that will remain at a temperaturesuflicient to crack the:

sprayed oil' itself, this adding" to the qiialntify of desirable. vaporsremovedfroriithesp 'r'a one, t i The pyrolysis methods hich' have beenair ines re applicable to many industries ln particular, manta:comprises a metho of refining permit ing in which crude oil is topped wrmeve asoliriej-a'ii d thensubjiicted' to the pyrolysisni'ethods de's ieaabov; The invention further inc des an apparatus forlthe pyrolysisoraymtxarsonaemn materials whichQcomprises in :combina'tfion, an enlared ves el adsptedtdflsup;

. taiiiin'g entrained sends, and means r r iaeadhein port afiuidizedbedof finely divided solids, a leading to said enlarged sepai'atory vessel,"has c"oni-' prising a slagging type combustion device connecting withsaid conduitfor generatin'ga hot stream of gasesrconta hyqmc'arbbmonsreeaingintesaid c n uit. er specifically, n one em oqiment, theinvention provides apparatuscomprising, in'combinatioihl icond it,aslaggi'ng type burner having a hot gasouuei coiinc 3b; to one and oft'he conduit, an enlargedvessd adapted? to support a fluidize be-('1 offinely, divided solids can: i eoted to the other and of said conduit,nah-s: rd; an is: (hiding finely divideds'oli era" point aloiig'thell rt if said manna ape means for mmaneing afiy' star;

; bonaceous material to" said condiiit at aipointf b tween' the point ofintroduction of solids thereto aiid the end of the conduit joined tosaid vessel. e a v In another embodiment, apparatus according toth'eirflyentionscornprises a' first s'eparatoiy' vessel, atse cond sep aratorjyvessel adapted to support a fluidized beater finely divided solids,first conduit mean f f transferring solids from; said first to saidsecond vessel, meansfor' intro ducing a hydrocarbonaceous feed into saidcoiid a slagging type combustion device, second conduit mess? joiningsaid combustion devicewith' said first separat yessel, 1 means forintroducings'olids from said second? separatory vessel tosaid'se'condconduit means and me ns for ,conveying solids'from said'first s'e'paratory vessel" to" saidburner. H e In both embodiments,theconduits may haveyerit c nstrictions or threats at the point wherethe hy rdcar bon feed is introduced, N g, f j By choice of properconditions of operatio nland (feed stock, a great variety of valuableproducts canbe pro;

diene, cy clopenta'di'ene, gasolene, benzene, toluene, Xylene,naphthalene, resin-formers, creosote oil, electrodegral de pitch, andcoke, and synthesis gas for the product of arm monia, methanol,synthetic fuels, and the likei 3 L V Inthe detailed description whichfollows, memes will be made to the accompanying 'drawings'in which:

Fig. 1 is a schematic flow diagram arose type'of pyrol ysis systemaccording to the invention Wherein lijotgase ous products of combustionare brought into direct contacttwiflh the hydrocarbonaceous feed, 7 g jFig. 2 is asche ma tic fiowdia'grarri of a second type Oli pyrolysissystem according to the invention' in,ubhicli'heat is transferred to thehydrocarbon feed' by mea nsof finely dividedsolids, v i h Fig, 3 is aschematic flow diagram showing elements, of a preferred type osetrde'nm' refining system usingj the prolysis system of Fig. 2, and I Hi Fig. 4 is aschematic flow diagram showing eleme s, of another typeofpetzroleum refining system also using Referring first to Fig. 1, a

assgses 7 to one embodiment of the invention, may comprise a U-, shapedconduit 3 extending between a cyclone burner 4 an enlarged separationvessel, or gasifier 5, suitable for containing a fluidized bed of finelydivided solids 6.

i A line 7, having a valve 27, is provided for feeding solids from thebed 6 to the burner 4. A line 8 is provided for introducing oxygen, air,or other oxygen-containing gas to the burner 4. The burner has adraw-off 28 for liquid slag.

' A line 9 is provided for introducing finely divided solids from thebed 6 to the conduit 3 at a point 10 downstream from the connectionbetween the conduit 3 and the burner 4.

The conduit 3 has a Venturi throat 2 and at the throat a line 1 isconnected to the conduit for the introduction of a hydrocarbonaceousfeed. A preheater 11 is furnished for preheating the feed.

"The gasifier 5 has an internal solids separator such as a cycloneseparator 12 lfor further separating entrained solids from the gaseousproducts emanating from the bed 6. A line 13 is provided for removingsuch products from the vessel.

To provide a means for controlling the temperature in bed 6, a heatexchanger 16 is provided, together with a line 14 leading from the bed 6to the heat exchanger 16. A valve 15 controls the fiow through. line 14.Cooled solids are returned from the heat exchanger 16 to conduit 3 bymeans of a line 17 and a valve 18. A line 19, having a valve 20, isprovided for withdrawing solids from line 17. A line 21, having a valve22, is arranged for the introduction of fiuidizing gas into line 17.

' In the preferred mode of operation, a fluidized bed 6 of finelydivided solids is established in separation vessel 5. These solids arepreferably coke, of the general type to be produced, but they may beother solid material, such for example as coal, lignite, or oil shale.The temperature in the vessel 5 is maintained between about 600 F. andabout 1800 F., preferably between about 800 F. and about 1700 F., andthe pressure between about p.s.i.g. and about 2000 p.s.i.g., preferablybetween about p.s.i.g. and about 300 p.s.i.g. A certain amount of thefinely divided solid material is continuously with- [drawn from the bed6 through line 7 and is fed to the cyclone burner 4, where it is burnedwith air or oxygen introduced through line 8. The hot gaseous productsof combustion from burner 4, at a temperature between about 1400 F. andabout 5000 F., preferably between about 2000" F. and about 3200 F.,enter conduit 3 and are mixed with additional carbonaceous solidswithdrawn from the bed 6 through line 9. These solids enter the conduit3 at point 10, and are entrained in the hot gases and serve to cool thegases, preferably to between about 1200 F. and about 2000" F. Thepressure of the gases at this point is between about 0 p.s.i.g. andabout 2050 p.s.i.g., preferably between about 6 p.s.i.g. and about 305p.s.i.g.

The mixture of hot products of combustion from burner 4 and solidparticles pass through the Venturi throat 2 where they pick up thehydrocarbonaceous feed, introduced from the line 1, after having beenpreheated in heater 11. Upon introduction of the feed into the conduit3, pyrolysis is initiated.

The temperature of the materials in the reaction zone downstream of theVenturi throat is between about 1100 F. and about 1800 R, preferablybetween about 1100 F. and about 1700 F. The pressure is maintainedbetween about 0 p.s.i.g. and about 2050 p.s.i.g., preferably betweenabout 6 p.s.i.g. and about 305 p.s.i.g.

As indicated generally above, in one embodiment of the invention, theendothermic part of the pyrolysis reaction is preferably completed inthe conduit 3. The exothermic part, on the other hand, may be carriedout in the conduit 3 or in the gasifier 5. Where the exothermic part iscarried out in the gasifier, the gasifier is operated at a temperaturebetween about 1100" F. and about 8 1800 F., preferably between about1100 F. and about 1700 F., and at a pressure between about 9 p.s.i.g.and about 2050 p.s.i.g.

Where the gasifier bed is used to quench the products of reaction, thegasifier, is operated at a temperature between about 600 F. and about1100 F., preferably between about 800 F. and about 1100 F., and at apressure between about 0 p.s.i.g. and about 2000 p.s.i.g., preferablybetween about 0 p.s.i.g. and about 300 p.s.i.g. Under these conditions,further reaction of the cracked products is suppressed and the heavypitch materials produced by the cracking reaction are condensed onto thesolid particles, leaving the cracked products to pass out overheadthrough cyclone separator 12 and line 13. The products emerging throughline 13 may be condensed and further treated, as for example bydistillation steps not shown.

To maintain the bed of fluidized particles 6 at proper temperature, astream of such particles may be withdrawn through line 14 and valve 15and passed through a heat exchanger 16 where it is cooled. The cooledmaterial is then returned to the bed 6 through line 17, valve 18, andconduit 3. If desired, a certain amount of this carbonaceous materialmay be withdrawn as product through line 19 and valve 20. To maintainthe proper fiow of material in line 17, a suitable fiuidizing gas, suchas steam, may be introduced through line 21 and valve 22.

The combustion carried out in burner 4 produces, in addition to the hotgases delivered to the conduit 3, a liquid slag which is withdrawnthrough off-take 28. This slag contains a large part of the corrosiveoxides originally present in the coke. The use of a combustion device,producing a liquid slag, thus furnishes a convenient way to prevent suchoxides from building up in the system and minimizes corrosion problems.

As noted above, the combustion-supporting gas introduced through line 8may be either air or oxygen. With air, a fuel gas can be produced havinga heating value in the neighborhood of 200 to 600 B.t.u. per cubic foot,depending on the type of material charged. Using air, the production ofmaterials such as 'a'cetylene and butadiene is favored because thediluting effect of the nitrogen results in a lowered partial pressure ofhydrocarbon. Such lower partial pressure favors net formation ofunsaturated compounds because of the reduced chance for polymerizationdue to the lowered concentration.

If it is desired, on the other hand, to have the product gas high inB.t.u. content, e.g. 600-1S00 B.t.u. per cubic foot, or have it mostsuitable for the recovery of ethylene, oxygen should be used instead ofair at point 8. The use of oxygen to support combustion in the cycloneburner 4 obviates compressing a product diluted with nitrogen to the 500to 700 pounds per square 'inch necessary to separate the ethylene fromother gases present.

In bringing the apparatus shown in the drawing on stream, steam may beintroduced through line 8 and finely divided coke having a particle sizebetween about 10 microns and about 0.1 inch introduced through line 23and valve 24. When the bed 6 has been filled to a sufiicient depth, airor oxygen is introduced through line 8 and additional coke is introducedto the conduit 3, through line 24 and valve 25. Only sufiicient oxygenor air is introduced to supply the proper amount of heating. Excessoxygen or air is avoided. Hydrocarbon feed is then slowly introducedthrough line 1. The hydrocarbon is converted into coke in the conduit 3and bed 6 builds up in the gasifier 5. The carbon introduced throughvalves 24 and 25 is then gradually reduced and valves 26 and 27 areopened to permit carbon particles from the bed 6 to How through lines 7and 9 and thence into the cyclone burner 4 and conduit 3 respectively.

As indicated above, the system described has great flexibility ofoperation. Thus for example, solid materials may be charged through line30 and admixed with a gas or liquid introduced through line 1 to thepreheater 11. sfiefi gaiias may inelude ayamcs'r sgsac eais 'iiiate'frial such as coal, ligni te, peat; bilsli'ale', or eves aninertu'raterial such assand. arerm 's'dc as, new, introdiloe'd iiithisinann'ei', may be carb in the duct 3 and Se haration vessel 5 to givegaseoiis iroducts and, a coke o'r char. Depending or the" quantity b foxyg'en' present in the separation yessfel a certain amount "of gasifition to carbon monxide may also occur,

" e1 .-e tlie solid is nori-calrbohac'eous, it forms L for the: cokeproduced from theliqiiid or gaseous ma t al'tofdebosit on. Iii thisinstance, it is desirable to lconibustion device other than the slaggingtype shown in the drawing.

1 is possible to dispense entirely vyithjreheater i1; Closing ofi Valve3 4 and charging fluid feed through line ai1d solid material throughline 31 v r desired, the hydrocarbonaceous material charged to thesystem may beentirely' solid material l ngtliis' eYeht, yalye 34 isclosed and the coal or simila solid y rq a n q fee ma r a i h r e .s 't3 bmi h. line 1 m ndiot e' v n r a b l ,i dueedjthrough line 33. to movethe finely divided solid to the duct 3;

" Aiurtherernbodirnent of the amended shown N Fig. 2. As shown in thatfigure, a system according the invention may comprise a g asifier 1'00haying an upper enlarged separating section 121 of r nore o'r lesscylindrieal sha 'ie and an elongated, ta' iere'd leg 101. The up- 156%edition 121 is adapted to support and contain afiu'idizedbed of finelydivided solids 106; Adjacent the gasifier are a burner, such as asla'gging-typeeyclone 102 and a cyclone separator 103. A duct 104 leadsfrom the exhaust end 105 of the burner 102k the cyclone separator 103'.Theburner has air inlet 107 and an outlet 108 for liquid'slag.A'trans'fer line 109 for flui diied solids leads frointhe bed 106 ingas'ifier 100 to the duct 104. A line 110 is provided supplyfluidiz'ilig' 'gasg su ch as steam, to the line 109 to maintain thesolids being transferred through that line in fluidized condition andtoaid in conveying the solids.

- Alinell l extends from the bottom of cyclone sepf arator 103 to thebottom of the leg 101 of the g'asifier 100 to enable solids to betransferred from the cyclone to the gas'ifier. Inert fluidizin: gas,e.'g. steam; may be furnished for this transterg through lines 112 and113; located on line 111 and aillie b0tt0lfi of leg 101, re spectively.Aline 122 is provided just down tream froni line 112 fortheintroduction' of material having a high I I/C ratio; such as recycledproduct gas. A feed line 114 for hydiocarbonacebus ndaterial is locatedat the bottom of leg 101 downstream from line 122 Sprays 124, fedthrou'gh a line 123 are furnished at the bottoifi o'f'theen1argedsection 121 of gasifier 100 for supplying oil to quenchthe'r'naterialsbeing 121 through 1e 101,

A line 115 extends between the cyclone separator 103 ahd the burner 102for furnishing solidstdthe cyclone burner; The inlet 119 for the line115 is preferably arranged on the Wall of the cyclone: 10$,s'6n11edistance u fro'in' its yerte'x, so that the solidsjfurhis'h'ed to theburner 102 are preferably larger than those drawn 011 the VertX of thecyclone for delivery tothe ga-sifier '100'.

' A d aw-be um; 116 is provided for ren'io'ving some' iir; the solidsmoving through line 115 Where it is desired to w I In a preferred methodof operating the system illiisirecover coke as a product.

trated in Fig. 2, a bed 106 of earbonaceous' solids, such as coke orchar having a particlesize between'iabout 10 microns and about 0.1 inchis established in" the upper section 121 of the gasifier Itis maintainedat be t v ven about 600 F. and about 1800 F; preferably betjv yeen about800 F and about 1700 F., the precise temperaturedepending on thereactantsQthe products 'de sired, and whether the bed is being used tIoquench or to complete the pyrolysis. The pressure is reprieve deliveredto the section A certa n One stream, havmg o ime-ice;

.. g i er r A v qly jis le i n r as t e n f fli substan es; t t fix ljsfibf m me sulphur @9 2: tent of the solidpyrolysrs' residue. Suchmaterials may e int dqcs th pu hl d te the bottom of leg 10]. f 4; 1 1?1 10 2,1: thi ad is usua ly d p ie a fi at h the gas introduced thin airor oxygen. V Hydrocarbonaceous grater-gal, liquid, gas or solid, is

fed'iht'o iii v hot" entrained solids th'rough'lirie'114 m or 101.Thi'simaterialf 5%? as 11's; a hdicok or whlch in Pa t de o the enim?Hel s ts ms ini g throiigh" use 118 may .2 1 shew; t e q i L- Thesolids" are withdrawn 101 the fluidized bed 106;" In such ar ang m'e'nt,the heat re lafsedidgififig the eirothernii'c pug he ps us maintain thetem erature offi'u'idiz d swat rea 'iQ'n' revs:

Altrnat ely; 56th pblfti ns 6f the pyrolysis can be ear: 4 5 bed" 106can be used to ced' below, as explained is degrees part of (l1 q 7 my beao; 'inplislidby' iiians of oil; 7E oily" snfinnd mraugu 124111111136123? Spraying oil at this point not only q lmches the products orpyrolysis, but also permits crackingbf 'materials such as gas oil, whichmay themselvies have been producedby the pyrolysis. The amount of. oilused is preferably limited to not more than that which will bring thetemperature of the gases down to th'bracking temperature of the oilbeing sprayed, e.g. to not less than 800 F. and preferably to 800-1200R, where the sprayed oil is 'gas' The composition of the hydrocarbonfeed charged through line 114 is subject to the same wide variation,which has been described in connection with Fig. 1.

As indicated above, the pyrolysis method and apparatus which have beendescribed may'bensed with great advantage in the refining ofpetroleum."' Two refining systems employing the novel methodandapparatus are shown schematically in Figs. Band 4.

Referring to Fig. 3, akrefihing' system according to the invention maycomprise a pyrolysis unit indicated generally as 200, and a fractionator201. The pyrolysis unit 200 is of the general type discussed above'inconnection with Fig. 2 and comprises 'a gasifier 202 having an enlargedupper section 203 "suitable for supporting a bed of fluidizedsolids,"and an elongated tapered lower leg 204, a cyclone burner 205, acyclone separator 206, and a duct 207 connecting the burner 205 and thesepa rator 206 with the bottom of thele'g 204'. A solids drawofl chamber209 is provided'on' a wall of the upper portion 203 of gasifier'202 andaline 210 connects this draw-'oif'chambe'r with the duct 207." An airinlet line 211 is provided for burner 205. Asolids draw-01f chamber 212is provided'on a wall of cyclone separator 206 and a line 213 connectsthis draw-offchamber with the air inlet line 211 to theburner 205." Aline 214 is provided for removing gases from separator 206.

' An internal cyclone 215 having a dip leg 216 is mounted in the uppersection 203 of gasifier 202 and a line 217 is provided to receive thegases discharged from gasifier 202 through this cyclone 21 5.

Fractionator 201 has an upper section 218 and a lower section 219,separated by an a'ccumulatorpan 220 having a chimney 220a. Each sectioncontains a number of trays 221. Thenumber and design of these traysdepends on various factors, such as the composition of the feed, and arereadily calculated by those skilled in the art. 0 i i A heat exchanger222 is set up adjacent the fractionator 201 and a line 223 is providedfor furnishing 'fluid from a tray in the bottom section 219 of thefractionator to the heat exchanger. A line 224 is arranged to return atleast a portion of this fluid to the fractionator and a line 225,connecting with this line 224, permits a portion of the fluid to bewithdrawn after passing through the heat exchanger 222.

A line 226 for crude oil feed passes through heat exchanger 222 anddischarges to the upper section 218 of the fractionator. Aline 227 isprovided for delivering liquid from the accumulator pan to the bottom ofthe leg 204 of gasifier 202. A line provided for withdrawing residuefrom the bottom of the lower sec tion 219 of the fractionator. This line228 has a branch 229 which joins the line 227, permitting at least aportion of the residue from the bottom of fractionator 201 to be chargedto the leg of the carbonizer. Another brarich 230 of line leads back tothe lower portion 219 of the fractionator, quenching the gaseousproducts of gasifier 202 discharging through line 217.

In operation, a fluidized bed or finely divided carbonaceous material,such as the coke produced in the process, is maintained in the uppersection 203 of carbonizcr 202. This bed is maintained at a temperaturebetween about 600 and 1800 E, preferably between about 800 and about1800, F. by withdrawing colge p odu d therein hr u line 19. ep n i omentt nins ases n separa or- 296mg" burni gs Par 9 the separated coke inburner 205, all as described above in connection with Fig. 2.

Crude oil is introduced through line 226. It is preheated in heatexchanger 222 and charged to the upper section 218 of fractionator 201.There, gasolene and lower boiling components are removed overheadthrough line 231. The residual liquid collects on accumulator pan 220and is charged through line 227 to the leg 204 of gasifier 202. Here itmeets a stream of inert gas, such as steam, introduced through lines 232and 233, and hot entrained solid coke particles, and is pyrolysed in theleg 204, or in the leg 204 and in the fluidized bed 234 to give coke anda mixture of gas oil, gasolene containing some aromatics, and fixedgases containing a high proportion of ethylene and other olefins. Theseproducts are removed through cyclone 215 and line 217 and meet theresiduum from fractionator 202 flowing through line 230 which serves toquench the high temperature gases. The combined stream of gases andresidue is returned to the lower section 219 of fractionator 201 wherefurther separation is carried out.

A side stream comprising naphthalene oil can be withdrawn from the lowersection 219 of the fractionator through line 223 and used to heat thecrude in heat exchanger 222. A part of this naphthalene oil can then bewithdrawn through line 225 and the balance returned to the fractionatorthrough line 224.

A part of the fuel oil residue from the lower section 219 offractionator 201 can be charged to the gasifier through branch 229 ofline 228. Another part may be withdrawn as product through line 235.

Another system for refining petroleum according to the invention isshown in Fig. 4. Again the system comprises a pyrolysis unit 300 and afractionator 301. The pyrolysis unit is similar in construction to thatshown in Fig. 3. It comprises a gasifier 302 having an enlarged uppersection 303 and an elongated lower leg 304, a separator 306 and a burner305. A duct 307 is provided for delivering hot gases from burner 305 toseparator 306, and a line 313a is arranged to deliver solids fromseparator 306 to burner 305 for use as fuel. Air or oxygen may be fed toburner 305 through line 311a. A line 308 carries hot solids from theseparator 306 to the gasifier 302 and a line 310 carries solids from thegasifier to duct 307. A line 337 is provided for supplying a gas havinga high H/C ratio, such as recycled product gas, to'the gasifier 302.

The fractionator 301 comprises a number of bubble trays 311 ofconventional design. A line 312 connects the top of gasifier 302 to apoint near the bottom of fractionator 301. A line 313 is provided forintroducing crude oil into line 312. Another line 314 connects thebottom of fractionator 301 with the bottom of gasifier leg 304. A gasoil side stream may be drawn off fractionator 301 through line 315. Apart of the gas oil may be sprayed through sprays 335 to quench the hotproducts of pyrolysis and crack the gas oil. The overhead from thefractionator is removed through line 316.

'In operation, a fluidized bed 334 is established in the upper section303 of gasifier 302 as described above in connection with Figs. 2 and 3.Crude oil is charged through line 313 and serves to quench the hot gasesemanating from the carbonizer. The combined stream is delivered tofractionator 301 where a gaseous stream, comprising fixed gases andgasolene, is removed overhead. Gas oil is removed as a side streamthrough line 315. A portion of this material is delivered to sprays 335where it serves to partially quench the hot products of pyrolysis to say800- 12O0 F. and is itself cracked to gasolene. The bottoms from thefractionator, comprising all components of the crude oil boiling aboveabout 350 F. are sent through line 314 to the bottom of car bonizer leg304 and into the fluidized bed 334. Recycled product gas may. be addedto the charge to bed 334 rou line 3 Using the apparatus of Fig. 1, 750barrels per hour of a Bunker C fuel oil are introduced into preheater 11and heated to about 600 F. About 20,000 pounds per hour of coke areburned with air in the burner 4 to give a tem perature at the outlet ofthe burner of about 3000" F. About 600,000 pounds per hours of coke areintroduced at point into conduit 3 to cool the hot gases from thehea'terto a temperature of about 1600 F. The tempera ture in thegasifier 5 is maintained at about 1200 F.

About 85,000 standard cubic feet per minute of volatile products arewithdrawn through line 13, having the following approximate analysisWeight percent Oil gas Aromatic liquids 20 Gombustion products 55 200pounds per hours of coke are withdrawnthrou'gh valve 20. h i Example IIJIhe procedure described in Example I is carried out ex cept thatoxygeniiistead of air is introduced through line 8. The temperature atthe outlet of the burner is about 4000F'. The temperature just upstreamfrom the .Venturi throat 2 is about 1700 F. and the temperature in theg'asifier is about 1150 F. The product removed through line 13 analyzesapproximately as follows:

H Weight percent Qlillsa'sj Aromatic liquids Combustion products V 305000 pounds of coke per hour are withdrawn through valve 20. i

' I Example 111 The' p'r' ee's'e described in Example I is carried out,but ab 17,000 standard cubic feet per minute of propane ea as thehydrocarbon feed. Approximately 3000 standardcubic feet per minute offuel gas are introduced to, cyclone burner, with suflicient air forcombustion. The te'rj nperatu re atv the outlet of the burner is about 3200fjF; About 400,000 pounds per hour of coke are removed from thegasifier through line 9 and introduced into the conduit at 10. Thetemperature just upstream tim t e Venturi throat 2 is about 1s0o F. Thetemp'ratur e in the bed 6 is about 1400 F. A small amount of coke isinterm'ittently removed through line 20. About 05,000 standard cubicfeet per minute of gaesous produt are removed through line 13, analyzingapproximately as follows Weight percent Oi s Afromatie liquids 5Combustion products Example V l00barrels per hour of a heavy Bunker Cfuel are introducedinto heater 11 in the syst en t of Fig. 1, and heatedto about 600 F. 100 tons per hour of drogen.

coal are added through valve 31 and the mixture is duced into the systemat point 2; About Buttons per hour of coke are gasified in burner 4using about 50,000 standard cubic feet per'minut of a mixture of oxygenand steam in about equal proportions, giving a temp ra: hire at theoutlet or about 2500 F- About 300,000 pounds per hour of coke areintroduced at point 10 i ntd conduit 3 to cool the hot gases from theheater to a te'r'n' perature of about 1600 F. The temperature in thegasifier 5 is maintained at about 700 F. in order to quench the gaeousproducts, to remove unstable compounds by reaction and to remove heavypitches by conden'sation onto the coke.

About 100,000 standard cubic feet per minute of volatile products arewithdrawn through line 13, having the following approximate analysis:

Weight percent Oil gas 12.5, Aromatic liquids 7.5 Partial combustionproducts 80.0 100.6

The partial combustion product contains over 30% hy Example V 1000barrels per hour of a Bunker C fuel oil are introduced into the systemof Fig. 2. About 3,510,000 pounds per hour of coke are withdrawnfrom thegasifier and charged to duct 104. 55,100 pounds pet: hour of this cokeare charged to burner 102 where they are burned with air to give a'liquid slag and hot combus tion products, and 3,440,000 pounds per hourare re cycled through line 111. 27,000 gallons per hour of gas oil aresprayed through sprays 124 into bed 106. The temperature in theg'asifier' bed is about 1300 F. About 66,000 standard cubic feet perminute of water-free volatile products are withdrawn through line 118,having th following approximate analysis:

Weight percent Oil s t .7 Aromatic distillates 21 Pitch 32 Example VIThe conditions of Example V are repeated, except additional fuel oil isburned in burner 102 to supplement the heat obtained from burningproduct coke, and about 37,000 standard cubic feet per minute ofrecycled prod uct gas having the following composition:

Percent CH 65 Heavier gases 5 are charged through line 1 22. Theresulting volatile products withdrawn through line 118 have thefollowing composition (on a recycle-gas free basis):

Example VII v 100,000 pounds per hour of bituminous coal, having thefollowing approximate analysis:

Weight percent Carbon 76 A h Volatile combustible matter 26 areintroduced through line 114 into the system of Fig. 2. Steam used as thefluidizing and conveying medium in line 113. The temperature of thegasifier bed is kept at 1300 F. 76,000 pounds per hour of char are drawnfrom cyclone 103 and returned via line 111 to the gasifier. Thewater-free gaseous product removed through line 118 amounts to around520,000 standard cubic feet per hour and has the following approximateanalysis:

Weight percent Coal gas 7 Aromatic liquids 27 Example VIII 1000 bbls.per hour of a 38 API mid-continent crude oil containing about 32%reduced crude after atmospheric distillation, is fed through line 226into fractionator 201 in the apparatus of Fig. 3. 600 bbls. per hour oftopped crude is removed from accumulator pan 220 and charged topyrolysis unit 200 along with 50 bbls. per hour of the fuel oil bottomsremoved from the lower section 219 of fractionator 201. A fluidized bedof petroleum coke at a temperature of about l 100 F. and pressure ofabout p.s.i.g. is maintained in carbonizer 202. Total products obtainedare (wt. percent of the crude):

- Weight percent Gas (ethylene about 24%; propylene and heavier,

18% by volume) 3,6 Gasolene Naphthalene oil 1 Fuel oil (viscosityequivalent to ASTM #6) l6 Coke 7 100 Example IX 1000 bbls. per hour ofthe same crude used in Example VIII are charged through line 313 in thesystem of Fig. 4. 400 bbls. per hour of bottoms from the fractionator301 are fed to gasifier 302. A fluidized bed of coke is maintained inthe gasifier at a temperature of about 1100 F. and a pressure of about25 p.s.i.g. 250 bbls. per hour of gas oil are recycled through line 336and sprays 335. Total products obtained are (approx. wt. percent of thecrude) Weight percent Gas 08-25% ethylene and up to total olefins) 15Gasolene 45 Gas oil 28 Coke -Q 12 Example X Example IX is repeatedexcept that 14,800 standard cubic feet per minute of recycled productgas having the following composition:

Percent H 30 CH; Heavier gases 5 From a consideration of the foregoingdescription, it will be seen that the invention provides a simple,direct, versatile and economical method and apparatus for the productionof gaseous, liquid, and solid products by pyrolysis of hydrocarbonaceousmaterials. Only one fluidized bed is required so that the initial costis lower and maintenance is reduced as compared with prior sys: terns.The necessary heat can be furnished by combustion of the coke produced,and this combustion is carried out under conditions which are flexibleand easy to control, and which permit corrosive oxides present in thefuel to be removed from the system. Pyrolysis of the hydrocarbonaceousfeed is done under conditions where deposition of coke on heat transfersurfaces is not aproblem.

The process described is inherently flexible in that the time andtemperatures of reaction can be readily and independently adjusted byvarying the length of the conduit, and the temperatures both in theconduit and in the separation zone. This ability is valuable especially.where it is desired to produce in optimum amounts the most valuableproducts by feeding stocks of varying character at different pointsalong the conduit, and where it is desired to produce certain relativelyunstable cornpounds such as butadiene, which require that the mate rialbe very quickly brought up to temperature, cracked for a relativelyshort time, and then quenched below the temperature at which thesecompounds will react with other material present, or polymerize.

The novel process is valuable in many industries. In particular, as inthe forms illustrated above, it can be used with great economy inpetroleum refineries of modcrate size.

What is claimed is:

1. A process for the pyrolysis of hydrocarbonaceous material whichcomprises charging a feed stream of hydrocarbonaceous material into ahot moving reaction stream of gases and entrained finely dividedcarbonaceous solids to heat said stream to between about 1100 F. and

about 1800 F. and to at least partially pyrolyse said. feed stream,delivering the combined feed and reaction streams to a fluidized bed ofsaid finely divided solids, removing vaporous products of pyrolysis fromsaid bed, removing carbonaceous solids from said bed, burning a firstportion of the solids removed from said bed in a combustion zone apartfrom a second portion of said solids removed from the bed to give hotgases and an ash"v residue, removing at least a portion of said residuefrom the process, contacting the second portion of the solids with thehot gases produced in said combustion zone to reheat said secondportion, and using the solids so reheated in forming said reactionstream.

2. The method claimed in claim 1 and in which the overall pyrolysisreaction has an endothermic part and an exothermic part, and comprisingconducting the endothermic part of the pyrolysis reaction in thereaction stream and the exothermic part in the fluidized bed.

3. The method claimed in claim 1 and comprising adding to the reactionstream a material selected from the group consisting of hydrogen andhydrocarbonaceous materials having a higher H/ C ratio than thehydrocarbona-. ceous feed.

4. The method claimed in claim 1 and comprising contacting the reactionstream with a quenching medium immediately prior to delivery to thefluidized bed. i

5. The method claimed in claim 4 wherein the quenching medium is ahydrocarbonaceous material and is itself at least partially crackedduring the quenching process.

6. The method claimed in claim 1 wherein the reaction stream is movedupwardly into the fluidized bed.

7. The process claimed in claim 1 in which the solids are burned underconditions such that a liquid slag is solids and thereby heating saidfeed stream to between about 1100 F. and about 1800 F., and at leastpartially pyrolysing said feed stream, delivering the combined feed andreaction streams to a fluidized bed of finely divided solids, removingvaporous products of pyrolysis from said bed, removing a first stream ofsolids from said bed, burning said first stream of solids in acombustion zone to form a high temperature stream of gaseous products ofcombustion and an ash residue, removing at least a portion of saidresidue from the process, removing a second stream of solids from saidbed and entraining solids from said second stream in said hightemperature stream of gaseous products of combustion to form saidreaction stream.

9. A process for the pyrolysis of hydrocarbonaceous material whichcomprises charging a hydrocarbonaceous feed material into a first movingreaction stream of gases and entrained, hot, finely divided carbonaceoussolids and thereby heating said feed to between about 1100 F. and about1800 F. and causing at least partial pyrolysis of said hydrocarbonaceousmaterial, delivering the combined feed and reaction stream to afluidized bed of finely divided solids, removing vaporous products ofpyrolysis from said bed, removing a stream of solids from said bed andentraining said solids in a second moving stream of hot gases, to heatsaid solids, delivering said second moving stream of hot gases with theheated solids entrained therein to a separating zone, removing hotsolids from said separating zone and burning said solids in a combustionzone to produce said second moving stream of hot gases and an ashresidue, removing at least a portion of said residue from the process,removing additional hot solids from said separating zone and entrainingsaid additional solids in a stream of gases to form said reactionstream.

10. The method claimed in claim 9 in which the finely divided solids aresolid products of pyrolysis.

11. The method claimed in claim 9 wherein the solids are burned underconditions such that a liquid slag is formed.

12. A process for the distillation of petroleum which comprises feedingcrude petroleum into a first moving stream of hot hydrocarbonaceousgases, fractionating the combined stream of crude petroleum and hotgases to give a product boiling above about 350 F., charging saidproduct to a hot moving stream of gases and entrained finely dividedcarbonaceous solids to heat said product to between about 1100 F. andabout 1800 F. and thereby at least partially pyrolyse said product,delivering the combined stream resulting from the step last referred to,to a fluidized bed of said finely divided solids, removing vaporizedproducts of pyrolysis from said bed, to form said first moving stream ofhot gases, removing solids from said bed, burning a first portion of thesolids removed from said bed in a combustion zone apart from a secondportion of said solids removed from said bed to give hot gases and anash residue, removing at least a portion of said residue from theprocess, contacting the second portion of the solids with the hot gasesproduced in the combustion zone to reheat the second portion and usingthe solids so reheated to form the hot moving stream of gases andentrained solids referred to.

13. A process for the refining of petroleum which comprises toppingcrude petroleum to remove a fraction comprising gasoline and lowerboiling materials, heating said topped crude to between about 1100 F.and about 1800 F. to at least partially pyrolyse said topped crude, bycharging said topped crude to a .hot moving reaction stream of gases andentrained carbonaceous solid particles, delivering the resultingcombined stream to a fluidized bed of said finely divided solidcarbonaceous particles, removing vaporous products of pyrolysis fromsaid bed, removing solids from said bed, burning a first portion of thesolids removed from said bed apart from a second portion of the solidsremoved from said bed to generate hot gases and to produce an ashresidue, removing at least a part of said ash residue from the process,contacting the hot gases so generated with said portion of the solidsremoved from said bed and thereby reheating said second portion ofsolids, and using the solids so reheated to form the first mentionedreaction stream.

14. The method claimed in claim 13 in which the solids are carbonaceousand are burned under conditions such that a liquid slag is formed.

15. The process claimed in claim 13 wherein the crude petroleum istopped by co-fractionation with the vaporized products of pyrolysis.

16. Apparatus for the pyrolysis of hydrocarbonaceous materialcomprising, in combination, a conduit having an inlet and an outlet, aslagging type combustion device having a hot gas outlet connected to theinlet of said conduit, a vessel adapted to support a fluidized bed offinely divided solids connected to the outlet of said conduit, means forconveying solids from said bed to said combustion device means forconveying finely divided solids from said vessel and introducing theminto said conduit at a point along its length and means for introducinga hydrocarbonaceous feed into said conduit at a point nearer to theoutlet of said conduit than the point of introduction of said finelydivided solids.

17. Apparatus for the pyrolysis of hydrocarbonaceous materialscomprising, in combination, a first separatory vessel, a second vesseladapted to support a fluidized bed of finely divided solids, firstconduit means for transferring solids from said first to said secondvessel, means for introducing a hydrocarbonaceous feed into said firstconduit means, a slagging type combustion device having a hot gasoutlet, second conduit means joining said hot gas outlet with said firstseparatory vessel, means for introducing solids from said second vesseldirectly into said second conduit means and means for conveying solidsfrom said first separatory vessel to said combustion device for burningtherein.

References Cited in the file of this patent UNlTED STATES PATENTS1,646,760 Miller Oct. 25, 1927 2,357,301 Bailey et al Sept. 5, 19442,485,315 Rex et al. Oct. 18, 1949 2,557,680 Odell June 19, 19512,700,017 Brown Jan. 18, 1955 2,700,642 Mattox Jan. 25, 1955 2,710,827Gornowski a- June 14, 1955 2,719,114 Lefler Sept. 27, 1955 2,734,020Brown Feb. 7, 1956 2,737,479 Nicholson Mar. 6, 1956 UNITED STATES PATENTOFFICE CERTIFICATE OF CORRECTION Patent No. 2,88-,,368 April 28, 1959Maxwell Patrick Sweeney It is hereby certified that error appears in theprinted specification of the above numbered patent requiring correctionand that the said Letters Patent should read as corrected below.

Column 10, line 1, for "2B0 p.,s.i.g, reed w 2000 p s,i.g., line '75,for "sparys" reed sprays column 11, line 18, for "Referring to Fig. 3"read m Referring first to Fig. 3 column 13, line '72, for

"Example V" read Example IV e Signed and sealed this 6th of October1959.

Attest:

KARL H. AXLINE ROBERT C. WATSON Commissioner of Patents AttestingOificer

1. A PROCESS FOR THE PYROLSIS OF HYDROCARBONACEOUS MATERIAL WHICHCOMPRISES CHARGING A FEED STREAM OF HYDROCARBONACEOUS MATERIAL INTO AHOT MOVING REACTION STREAM OF GASES AND ENTRAINED FINELY DIVIDEDCARBONACEOUS SOLIDS TO HEAT SAID STREAM TO BETWEEN ABOUT 1100*F. ANDABOUT 1800*F. AND TO AT LEAST PARTIALLY PYROLYSE SAID FEED STREAM,DELIVERING THE COMBINED FEED AND REACTION STREAMS TO A FLUIDIZED BED OFSAID FINELY DIVIDED SOLIDS, REMOVING VAPOROUS PRODUCTS OF PYROLYSIS FROMSAID BED, REMOVING CARBONACEOUS SOLIDS FROM SAID BED, BURNING A FIRSTPORTION OF THE SOLIDS REMOVED FROM SAID BED IN A COMBUSTION ZONE APARTFROM A SECOND PORTION OF SAID SOLIDS REMOVED FROM THE BED TO GIVE HOTGASES AND AN ASH RESIDUE, REMOVING AT LEAST A PORTION OF SAID RESIDUEFROM THE PROCESS, CONTACTING THE SECOND PORTION OF THE SOLIDS WITH THEHOT GASES PRODUCED IN SAID COMBUSTION ZONE TO REHEAT SAID SECONDPORTION, AND USING THE SOLIDS SO REHEATED IN FORMING SAID REACTIONSTREAM.